Synthesis and Reactivity of Transition Metal Hydrides

Michael Heinekey博士，华盛顿大学化学系，受到无机、生物无机和有机金属化学项目的支持，研究过渡金属氢化物的合成和反应性。开发铁钌阳离子二氢配合物的合成方法。这些配合物将作为氢化酶活性位点的模型进行研究。三吡唑基和相关的配体将用于稳定一系列阳离子Ir和Rh氢化物，这些氢化物将用于激活碳氢化合物。我们将研究发生在多氢化物金属配合物中的量子力学质子隧穿的结构和电荷依赖性，以增加对这一过程的机理理解。这项研究的一个重要部分将涉及到氘或氚已纳入氢化物的研究。氚核磁共振将被用来表征其中一些系统的行为。交换耦合将被发展为在这些系统中发生的溶剂化和离子配对的探针。在17.6特斯拉的高磁场下，研究了二氢配合物部分取向的发生，这些数据将用于确定配合物的H-H距离。氢分子与金属原子相互作用时可能被激活。这种行为在实验室和工业化学中具有巨大的效用，可以增加氢进行许多反应的能力，包括几乎所有的“氢化”反应。另一方面，随着人们对氢作为清洁燃料的兴趣的增加，氢与金属之间的相互作用已成为一个重要的话题。在这个项目中，氢附着在金属上的基本方式将被研究，氢原子如何相互交换以及与周围环境相互作用的细节将被确定。

Dr. Michael Heinekey, Chemistry Department, University of Washington, is supported by the Inorganic, Bioinorganic, and Organometallic Chemistry Program for studies of the synthesis and reactivity of transition metal hydrides. Synthetic methods will be developed for cationic dihydrogen complexes of iron and ruthenium. These complexes will be studied as models for the active site of hydrogenase. Tris-pyrazolyl and related ligands will be used to stabilize a series of cationic Ir and Rh hydrides that will be used to activate hydrocarbons. Structural and charge dependence of the quantum mechanical proton tunneling that occurs in polyhydride metal complexes will be investigated to increase the mechanistic understanding of the process. A significant portion of the study will involve the study of hydrides into which deuterium or tritium has been incorporated. Tritium nmr will be used to characterize the behavior of some of these systems. Exchange coupling will be developed as a probe of the solvation and ion-pairing that occurs in these systems. The occurrence of partial orientation of dihydrogen complexes in very high magnetic fields will investigated at 17.6 Tesla and these data will be used to determine the H-H distance in the complexes. Hydrogen molecules may be activated when they interact with metal atoms. This behavior has tremendous utility in laboratory and industrial chemistry to increase the ability of hydrogen to undergo many reactions, including virtually all "hydrogenation" reactions. In another respect, the interactions between hydrogen and metals has become an important topic with the increased interest in hydrogen as a clean fuel. In this project the fundamental ways that hydrogen becomes attached to a metal will be investigated and the details of how hydrogen atoms interchange with each other and interact with the surrounding environment will be determined.